Stabilizer mixture

ABSTRACT

Mixtures of compounds comprising a compound G 2  and at least one further compound from the group G 0 , G 1 , G 3 , G 4 , G 5 , G 6 , the compounds G 0 -G 6  corresponding to formula (I) in which, in the compound G 0 , the radicals R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are each hydrogen; G 1 , the radical R 1  is Q and R 2 , R 3 , R 4 , R 5  and R 6  are each hydrogen; G 2 , the radicals R 1  and R 2  independently of one another are each Q and R 3 , R 4 , R 5  and R 6  are each hydrogen; G 3  the radicals R 1 , R 2  and R 3  independently of one another are each Q and R 4 , R 5  and R 6  are each hydrogen; G 4 , the radicals R 1 , R 2 , R 3  and R 4  independently of one another are each Q and R 5  and R 6  are each hydrogen; G 5 , the radicals R 1 , R 2 , R 3 , R 4  and R 5  independently of one another are each Q and R 6  is hydrogen; G 6 , the radicals R 1 , R 2 , R 3 , R 4 , R 5  and R 6  independently of one another are each Q; and Q and the other symbols are as defined in claim 1, are effective as stabilizers for organic material with respect to damaging exposure to light, oxygen and/or heat.

The present invention relates to a stabilizer comprising a mixture of2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazines with at least 2 types ofindividual compounds, namely those in which 2 of the 6 hydroxyl groupshave been replaced by a hydrocarbyloxy radical, and at least one furthertype in which fewer and/or more than 2 of the 6 hydroxyl groups havebeen replaced by a hydrocarbyloxy radical. The invention likewiserelates to its use for stabilizing organic material, to a correspondingcomposition and method for stabilizing organic material, and toindividual novel compounds.

Individual compounds of the hydroxyphenyltriazine type which are derivedfrom 2,4,6-tris(2,4-diphenyl)1,3,5-triazine and their use as stabilizersare described, inter alia, in GB-A-975966, U.S. Pat. No. 3,113,940, U.S.Pat. No. 3,113,941, U.S. Pat. No. 3,113,942, CH-A-467833, U.S. Pat. No.3,244,708. U.S. Pat. No. 3,249,608, EP-A-434608, U.S. Pat. No.5,300,414, U.S. Pat. No. 5,489,503, GB-A-2319523, GB-A-2337049,CH-A484695.

Certain mixtures of hydroxyphenyltriazines have also already beenproposed as stabilizers, for example in EP-A-444323, GB-A-2317893, U.S.Pat. No. 5,668,200.

Mixtures of compounds have now been found which possess surprisinglyadvantageous properties. The invention therefore firstly provides amixture comprising a compound G₂ and at least one further compound fromthe group G₀, G₁, G₃, G₄, G₅, G₆, the compounds G₈-G₈ each correspondingto the formula I

in which

-   X, Y and Z independently of one another are H, T₁, OT₁, NT₁T₂, ST₁,    SOT₁, SO₂T₁, SO₂NT₁T₂, SO₃H, SO₃T₁, SO₃M or -D; where-   T₁ and T₂ are C₁-C₅₀alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl,    C₇-C₁₈alkylaryl, C₆-C₁₈aryl, C₂-C₅₀alkenyl, C₅-C₁₂cycloalkeny,    C₂-C₅₀cycloalkynyl, C₅-C₁₂bicycloalkynyl, C₅-C₁₈bicycloalkyl,    C₆-C₁₈bicycloalkenyl; or one of these radicals substituted by one or    more D and/or, if desired, interrupted by one or more units E;-   D is selected from —R, —OH, —OR, —SR, —NRR′, —NRSO₂R₁, —SOR, —SO₂R,    —SO₂NRR′, —SO₃H, —SO₃M, —SO₃R, oxiranyl, -Hal, —CN, —COR, —COOR,    —COOM, —CONRR′, —OCOR, —OCOOR, —OCONRR′, —NRCOR′, —NRCOOR′,    —NRCONR′R″;-   E is selected from —O—, —S—, —NR—, —SO—, —SO₂—, —SO₂NR—, —CO—,    —COO—, —CONR—, —OCO—, —O——CO—O—, OCONR—, —NRCO—, —NRCO—O— and    —NRCONR′—;-   R, R′, R″, R* independently of one another are H, C₁-C₅₀alkyl,    c₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl, C₇-C₁₈alkylaryl, C₆-C₁₈aryl,    C₂-C₅₀alkenyl, C₅-C₁₂cycloalkenyl, C₂-C₅₀alkynyl,    C₅-C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl, C₆-C₁₈bicycloalkenyl; or are    one of these aforementioned hydrocarbon radicals substituted by OH    and/or interrupted by O;-   Hal is —F, —Cl, —Br or —I;-   M is a monovalent metal cation, preferably an alkali metal cation,    or is N(RR′R″R*)⁺, especially ammonium, or is P(RR′R″R*)⁺:-   and in which, in the compound-   G₀, the radicals R₁, R₂, R₃, R₄, R₅ and R₆ are each hydrogen;-   G₁, one radical from the group R₁, R₂, R₃, R₄, R₅ and R₆ is Q and    the others are each hydrogen;-   G₂, two radicals from the group R₁, R₂, R₃, R₄, R₅ and R₆ are each Q    and the others are each hydrogen;-   G₃, three radicals from the group R₁, R₂, R₃, R₄, R₅ and R₆ are each    Q and the others are each hydrogen;-   G₄, four radicals from the group R₁, R₂, R₃, R₄, R₅ and R₆ are each    Q and the others are each hydrogen;-   G₅, five radicals from the group R₁, R₂, R₃, R₄, R₅ and R₆ are each    Q and 1 radical is hydrogen;-   G₆, the radicals R₁, A₂, R₃, R₄, R₅ and R₆ are each 0; and-   Q is —T₁, —COT₁, —COH₁, —COOT₁, —CONHT₁, —CONH₂ or —CONT₁T₂.

Preferred mixtures are those in which, in the compound

-   G₀, the radicals R₁, R₂, R₃, R₄, R₅ and R₆ are each hydrogen;-   G₁, the radical R₁ is Q and R₂, R₃, R₄, R₅ and R₆ are each hydrogen;-   G₂, the radicals R₁ and R₂ independently of one another are each Q    and R₃, R₄, R₅ and R₆ are each hydrogen;-   G₃, the radicals R₁, R₂ and R₃ independently of one another are each    Q and R₄, R₅ and R₅ are each hydrogen;-   G₄, the radicals R₁, R₂, R₃ and R₄ independently of one another are    each Q and R₅ and R₆ are each hydrogen;-   G₅, the radicals R₁, R₂, R₃, R₄ and R₅ independently of one another    are each Q and R₆ is hydrogen; and-   G₆, the radicals R₁, R₂, R₃, R₄, R₅ and R₆ independently of one    another are each Q.

C₁-C₅₀alkyl, for example T₁, T₂, R, R′, R* or R″, is a branched orunbranched radical such as for example methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl,isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl,n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl,3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl,1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methyl-undecyl,dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl. One of the preferreddefinitions is for example C₂-C₁₈alkyl. A particularly preferreddefinition of R, R′ and R″ is C₁-C₄alkyl.

T₁, T₂, R, R′, R* and R″ as C₅-C₁₂cycloalkyl are for examplecyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cyclododecyl. Cyclohexyl and cyclododecyl are preferred.

T₁, T₂, R, R′, R* and R″ as C₇-C₁₈arylalkyl are for example benzyl,methylbenzyl, cumyl.

T₁, T₂, R, R′, R* and R″ as C₇-C₁₈alkylaryl are for examplemethylphenyl, dimethylphenyl, mesityl, ethylphenyl, propylphenyl,butylphenyl, dibutylphenyl, pentylphenyl, hexylphenyl, heptylphenyl,octylphenyl.

T₁, T₂, R, R′, R* and R″ as C₆-C₁₈aryl are for example phenyl, naphthyl,biphenylyl. Phenyl is preferred.

T₁, T₂, R, R′, R* and R″ as C₂-C₅₀alkenyl are for example vinyl, allyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl; preference is given toallyl if the radical binds to a heteroatom (an atom other than carbon.e.g. O), and vinyl where the radical binds to carbon.

A preferred definition of D as OCOR is acryloyloxy or methacryloyloxy.

T₁, T₂, R, R′, R* and R″ as C₅-C₁₂cycloalkenyl is preferablycyclohexenyl.

T₁, T₂, R, R′, R* and R″ as C₂-C₅₀alkynyl is preferably propargyl.

T₁, T₂, R, R′, R* and R″ as C₅-C₁₂cycloalkynyl is for examplecyclohexynyl.

T₁, T₂, R, R′, R* and R″ as C₅C₁₈bicycloalkyl is for examplebicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl (norbornyl).

T₁, T₂, R, R′, R* and R″ as C₆-C₁₈bicycloalkenyl is for examplebicyclo[2.2.1]hept-2-enyl, bicyclo[2.2.2]octenyl (norbornenyl).

Oxiranyl is an epoxy radical of the formula

it is preferably attached to CH₂ and so forms a glycidyl radical.

As described above, the aforementioned radicals may be substituted by Dand/or, if desired, interrupted by E. Interruptions are of coursepossible only in the case of radicals containing at least 2 carbon atomsconnected to one another by single bonds; C₆-C₁₈aryl is not interrupted;interrupted arylalkyl or alkylaryl contains the unit E in the alkylmoiety.

D₁ are carbon-bonding substituents D: —R, —CN, —COR, —COOR, —COOM,—CONRR′; D are heteroatom-bonding substituents D: —OH, —OR, —SR, —NRR′,—NRSO₂R′, —SOR, —SO₂R, —SO₂NRR′, —SO₃H, —SAM, -Hal, —OCOR, OCOOR,—OCONRR′, —NRCOR′, NRCOOR′, —NRCONR′R″.

D₂-substituted acyclic radicals contain preferably 2 or more, especially2-18, carbon atoms. D₂ is generally not attached in the α position.

Acyclic radicals, where interrupted, contain preferably 3 or more,especially 318, carbon atoms. In general, T₁ or T₂ as interruptedradicals contain 2 or more carbon atoms for each interrupting unit E. Ingeneral, not more than 1 interrupting unit E is inserted into a C—Csingle bond, avoiding accumulations of the type —E—E—. Asymmetric E maybe present in any position; for example, E as —CO—O—embraces both esters(in which —CO is aligned facing the molecule core) and retroesters (inwhich —O— is aligned facing the molecule core).

Hal is for example fluorine, chlorine or bromine or iodine. Chlorine ispreferred.

Alkyl is for example C₁-C₁₈alkyl like methyl, ethyl, propyl, isopropyl,butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl or octadecyl. Cycloalkyl is mainly C₅-C₁₂ cycloalkyl likecyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl.Alkenyl stands within the definitions given inter alia for vinyl, allyl,1- or 2-butenyl etc. The residues defined, where appropriate, may bestraight or branched chain. Polyvalent residues are derived from thecorresponding monovalent residues by abstraction of a H-atom; thus,C₁-C₁₈alkenylen stands, for example, for methylene, ethylene,ethylidene, 1,1-, 1,2- or α,ω-propylene, or the corresponding butylene,pentylene, hexylene, heptylene, octylene etc. isomers.

T₁ or T₂ as C₁-C₅₀alkyl substituted by one or more D and/or interruptedby one or more units E are for example (CH₂CH₂O)_(n)—R_(x), where n is anumber from the range 1-20 and R_(x) is H or C₁-C₁₀alkyl orC₂-C₁₀alkanoyl (e.g. CO—CH(C₂H₅)C₄H₉),

-   CH₂—CH(OR_(y)′)-CH₂—O-R_(y), where R_(y) is C₁-C₁₈alkyl,    C₅-C₁₂cycloalkyl, phenyl, C₇-C₁₅phenylalkyl, and R_(y)′ embraces the    same definitions as R_(y) or is H;-   C₁-C₈alkylene-COO—R₁, e.g. CH₂COOR, CH(CH₃)COOR₂, C(CH₃)₂COOR₂,    where R₂ is H, C₁-C₁₈alkyl, (CH₂CH₂)₁₋₁₅-R_(x) and R_(x) embraces    the definitions indicated above;-   C₁-C₁₂alkylene-SO₃H; CH₂CH₂—O—CO—CH═CH₂;    CH₂CH(OH)CH₂—O—CO—C(CH₃)═CH₂.

T₁ and T₂ are preferably, independently of one another, C₁-C₁₈alkyl,C₅-C₁₋₂cycloalkyl, C₇-C₁₈-phenylalkyl, C₇-C₁₈alkylphenyl, phenyl,naphthyl, biphenylyl, C₂-C₁₈alkenyl, C₅-C₁₂-cycloalkenyl, C₂-C₁₂alkynyl; or are C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₈phenylalkyl,C₇-C₁₈-alkylphenyl, phenyl, naphthyl, biphenylyl, C₂-C₁₈alkenyl,C₅-C₁₂cycloalkenyl, C₂-C₁₂alkynyl in each case substituted by one ormore D; or are C₂-C₅₀alkyl, C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl orC₇-C₁₈alkenyl interrupted by one or more E; or are C₃-C₅₀alkyl orC₄-C₁₈alkenyl or C₇-C₁₈-phenylalkyl which is substituted by D andinterrupted by E; especially C₁-C₁₈lalkyl, C₅-C₁₂cycloalkyl,C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl, naphthyl, biphenylyl,C₂-C₁₈alkenyl, cyclohexenyl; or C₁-C₁₈alkyl, cyclohexyl, cyclododecyl,C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl, naphthyl, biphenylyl,C₂-C₁₈alkenyl or cyclohexenyl in each case substituted by one or more D;or C₂-C₅₀alkyl, C₇-C₁₈phenylalkyl, C₇C₁₈alkylphenyl or C₄-C₁₈alkenylinterrupted by one or more E; or are C₃C₅₀alkyl or C₄-C₁₈alkenyl orC₇-C₁₈phenylalkyl which are substituted by D and interrupted by E.

Substituted cycloalkyl is for example methylcyclopentyl,dimethylcyclopentyl, methylcyclo-hexyl, hydroxycyclohexyl,carboxycyclohexyl, alkoxycarbonylcyclohexyl, dimethylcyclohexyl,trimethylcyclohexyl, tert-butylcyclohexyl.

M as monovalent metal cation may also be a positively charged metalcomplex; it is preferably an alkali metal cation, for example of themetals U, Na, K, Cs; in particular Na. M as N(R)₄+is preferably ammonium(NH₄)⁺.

X, Y and Z in preferred mixtures are each hydrogen, -T₁ or D, especiallyH.

A group of compounds of the formula I of particular technical interestis that in which X, Y and Z are each hydrogen and Q has the definitionT₁.

Of particular significance is a mixture of compounds in which G₂ and afurther compound from the group G₀, G₁, G₃, G₄, G₅, G₆ are each presentin an amount of from 1 to 99 parts by weight, for example 1-90 or 1-80parts by weight, especially 5-80 parts by weight, based in each case on100 parts by weight of the total compounds G₀-G₆ present in the mixture.

Preferred mixtures of compounds comprise, besides G₂, 2 furthercompounds from the group G₀-G₆, especially G₂, G₃ and G₄, each in anamount of from 1 to 98 parts by weight, based on 100 parts by weight ofthe total compounds present in the mixture. Mixtures of compounds whichare likewise preferred comprise Go, G₁ and G₂, or, with particularpreference, G₁, G₂ and G₃ each in an amount of from 1 to 98 parts byweight, based on 100 parts by weight of the total compounds present inthe mixture. Particularly preferred mixtures of compounds comprise,besides G₂, 3 further compounds from the group G₈₋G₀, for example G₁,G₂, G₃ and G₄, especially G₁, G₂, G₃, G₄ and G₅, each in an amount offrom 1 to 97 parts by weight, based on 100 parts by weight of the totalcompounds present in the mixture. Proportions of the individualcompounds which are of particular interest are in each case 1-90,especially 1-80 parts by weight, in particular 580 parts by weight,based on 100 parts by weight of the total compounds G₀-G₆ present in themixture.

Preferred components of the mixture of compounds of the invention arethose in which

-   X, Y and Z independently of one another are —H, —T₁, or D;-   T₁ and T₂ independently of one another are C₁-C₁₈alkyl,    C₅-C₁₂cycloalkyl, C₇C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl,    naphthyl, biphenylyl, C₂C₁₈alkenyl, C₅-C₁₂cycloalkenyl,    C₂-C₁₂-alkynyl; or are C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl,    C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl, naphthyl, biphenylyl,    C₂-C₁₈alkenyl, C₅-C₁₂cycloalkenyl, C₂-C₁₂alkynyl in each case    substituted by one or more D; or are C₂-C₅₀alkyl, C₇-C₁₈phenylalkyl,    C₇-C₁₈alkylphenyl, C₅-C₁₂-cycloalkyl, C₅-C₁₂cycloalkenyl or    C₄-C₁₈alkenyl in each case interrupted by one or more E; or are    C₂-C₅₀alkyl, C₃-C₁₈alkenyl, C₇-C₁₈alkylphenyl, C₅-C₁₂cycloalkyl, C₅    C₁₂cycloalkenyl or C₇C₁₈phenylalkyl which are substituted by D and    interrupted by E;-   D is —R, —OH, —OR, —NRR′, -Hal, —CN, —COR, —COOR, —COOM, —CONRR′,    —OCOR, —OCOOR, —OCONRR′, —NRCOR′, —NRCOOR′, —NRCONR′R″, oxiranyl,    —SO₃H, —SO₃M;-   E is —O—, —NR—, —CO—, COO—, —CONR—, —OCO—, —OCOO—, OCONR—, —NRCO—,    —NRCOO—, —NRCONR′-;-   R, R′, R″, R* Independently of one another are H, C₁-C₅₀alkyl,    C₅-C₁₂cycloalkyl, C₇-C₁₈ phenylalkyl, C₇-C₁₈alkylphenyl, phenyl,    naphthyl, biphenylyl, C₂-C₅₀alkenyl, C₅-C₁₂-cycloalkenyl,    C₂-C₅₀alkynyl;-   Hal is —F or —Cl; and-   M is an alkali metal cation or N(RR′R″R*).

T₁, T₂ and also R, R′, R* and R″ may independently of one another bestraight-chain or branched.

Particularly preferred components of the mixture of compounds of theinvention are those in which

-   Q is —Ts, —COT, or —CONT₁T₂;-   X, Y and Z independently of one another are —H, —T₁, D;-   D is —R, —OH, —OR, -Hal, —COR, —COOR, —COOM, —CONRR′, —OCOR, —OCOOR,    —OCONRR′, —SO₃H, —SO₃M;-   E is 4, —C, —COO—, —CONR—, —OCO—, —OCO—, OCONR—;-   R R′, R″ independently of one another are H, C₁-C₁₈alkyl,    cyclohexyl, cyclododecyl, C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl,    phenyl, C₂-C₁₂alkenyl; and-   Hal is —F or —Cl; and-   M is Li, Na or K.

Compounds of the mixture of compounds of the invention that arepreferred in particular are those in which

-   Q is —T₁, —COT₁, —CONT₁T₂;-   X, Y and Z independently of one another are —H, —T₁ or —D;-   T₁ and T₂ independently of one another are C₁-C₁₈alkyl,    C₅-C₁₂cycloalkyl, C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl,    naphthyl, biphenylyl, C₂-C₁₈alkenyl; or are C₁-C₁₋₈alkyl,    cyclohexyl, C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl,    C₃-C₁₂alkenyl in each case substituted by D; or are C₃-C₅₀alkyl,    C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl or C₄-C₁₈alkenyl interrupted by    E; or are C₂-C₅₀alkyl or C₄-C₁₈alkenyl or C₇-C₁₈phenylalkyl which    are substituted by D and interrupted by E;-   D is —R, —OH, —OR, -Hal, —COR″, COOR, —COOM, —OCOR″, —SO₃H, —SO₃M;-   E is —O—, —CO—, —COO—, —OCO—;-   R is H, C₁-C₁₈alkyl, cyclohexyl, C₇-C₁₈phenylalkyl,    C₇-C₁₈alkylphenyl, phenyl, C₃-C₁₂alkenyl;-   R″ is H, C₁-C₁₈alkyl, cyclohexyl, C₇-C₁₈phenylalkyl,    C₇-C₁₈alkylphenyl, phenyl, C₃C₁₂alkenyl;-   Hal is —F or —Cl; and-   M is Li, Na or K,    especially those in which-   Q is —T₁; X, Y and Z independently of one another are —H,    C₁-C₁₂alkyl, C₇-C₉phenylalkyl or C₃-C₆alkenyl; and T₁ and T₂    independently of one another are C₁-C₁₈alkyl, C₅-C₁₂cycloalky,    C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl, naphthyl, biphenylyl,    C₂-C₁₈alkenyl; or are C₁-C₁₈alkyl, cyclohexyl, C₇C₁₈phenylalkyl,    C₇-C₁₈alkylphenyl, phenyl, C₃-C₁₂alkenyl in each case substituted by    D.

Components G₀-G₈ of the mixture of compounds of the invention may beprepared by known methods or in analogy to such methods. Such methodsare described, for example, in GB-A-975966, CH-A484695. The compounds ofthe formula I may also be prepared in analogy to one of the methodsspecified in EP-A-434608, one of the publications mentioned at theoutset, or in the publication by H. Brunetti and C. E. Luthi, Helv.Chim. Acta 55, 1566 (1972). The starting point is oloudiciously thecompound 2,4,6tris(2,4-dihydroxyphenyl)1,3,5-triazine(trisresorcinoltriazine) or an appropriately substituted derivative ofthis compound (G₀, starting compound of the formula II). The startingcompound of formula II

may be prepared, for example, in analogy to EP-A-165608 by means ofFriedel-Crafts Reaction of cyanuric chloride or cyanuric halide and thecorresponding resorcinol derivatives (which already contain substituentsX, Y and Z), X, Y and Z being as defined above.

Unsubstituted trisresorcinoltriazine may also be substitutedsubsequently by introducing the groups X, Y and Z.

The starting compound of the formula II may be reacted further inaccordance with known methods to give compounds G₁-G₆ of formula I; suchreactions and methods are described, for example, in EP-A-434 608, page15, line 11, to page 17, line 1. Where organic halides Hal-Q orsulfonates Ts-SO₃-Q in which Hal is a halogen atom and Ts is for example4-tosyl or methyl are used for reaction with the free phenolic OH of thecompound G₀, the reaction is oudiciously conducted in the presence of anacid binding agent and an appropriate solvent. The use of aprolicsolvents such as diglyme for example is advantageous. Preference isgiven to the solvents dimethyl sulfoxide, dimethylformamide (DMF),dimethylacetamide, acetone, ethyl methyl ketone, ethanol, methanol,isopropanol, diglyme, water, toluene, xylene, and mixtures thereof.Established acid binding agents include bases such as carbonates andbicarbonates or alkoxides, such as Na₂CO₃, K₂CO₃, Na ethoxide, Namethoxide or potassium tert-butoxide, or metal hydrides. The productsmay be worked up in conventional manner, for example by separating offthe solvent and/or carrying out crystallization and/or distillation.

Alternatively, cyanuric chloride or cyanuric halide may be reacted with3 equivalents of a resorcinol derivative of the formula

for example In analogy to EP-A-165608, to give G₆ which can subsequentlybe reacted further by cleaving some of the bonds O-Q (e.g. dealkylationby means of AlCl₃) to give compounds of the type G₀-G₅ or of the mixtureof the invention.

The stabilizer of the invention may subsequently be obtained by mixing acompound of the type G₂ of formula I with at least one further compoundof type G₀, G₁ and/or G₃-G₈ as described earlier on above.

It is particularly advantageous to direct the alkylation or acylationstep in such a way that the desired mixture is formed starting fromcompounds of the formula II. This is the preferred route for preparingmixtures of the formula II. For this purpose, the abovementionedstarting compound of the formula II is judiciously reacted as describedwith Hal-Q, advantageously in the presence of a base (e.g. carbonates orhydroxides of alkali metals or alkaline earth metals such as Na, K, Ca,or ammonia or amines such as triethylamine, dibutylamine ortributylamine, etc.) and of appropriate solvent, examples being thosedescribed above; particularly preferred solvents are dimethylformamide(DMF), dimethylacetamide, N-methylpyrrolidone. Besides this solvent itis also possible to use a cosolvent, advantageously selected fromaliphatic or aromatic hydrocarbons, esters or ketones, such as heptane,benzene, toluene, xylene, butyl acetate, ethyl acetate, ethyl methylketone, methyl isobutyl ketone. For the reaction, it is preferred tocarry out heating with stirring, for example at 40-200° C., inparticular at 80-150° C., often for a duration of 1-10 h, especially2-8h. The desired degree of reaction is judiciously monitored by meansof customary analytical methods, such as thin layer chromatography (TLC)or high performance liquid chromatography (HPLC), and the reaction isterminated when the desired degree of reaction is reached, terminationbeing effective, for example, by temperature reduction, addition ofwater, and/or neutralization. It is possible for further reaction stepsto follow, examples being transesterification, saponification, saltformation, esterification, etherification. The mixture of compounds ofthe invention is subsequently obtained, usually following removal ofsalts and/or solvent(s), in some cases following extraction of theaqueous mixture with an appropriate organic solvent. Appropriateextractants in turn are the substances listed above as possiblecosolvents. An advantage of this method is that the product thusobtained can generally be used as a stabilizer without furtherpurification. It is also possible to use the mixture obtained directlyfrom the synthesis.

In certain cases a downstream purification step may also be ofadvantage: for example, the filtration of the solution of the mixture ofproducts, judiciously originating from the extraction, over a filter aid(e.g. magnesium sulfate, sodium sulfate, aluminium oxide, clay,activated carbon, silica gel, etc.), especially when an improvement incolour or lightening of the product mixture is desired. Distillation,precipitation and recrystallization are likewise possible forpurification.

Certain constituents of the mixture of the invention are novelcompounds. The invention therefore additionally provides compounds ofthe type G₁, G₂, G₃, G₄, G₅ and G₆ of the formula III

in which

-   X, Y and Z independently of one another are H, T₁, OT₁, NT₁T₂, ST₁,    SOT₁, SO₂T₁, SO₂NT₁T₂, SO₃H, SO₃T₁, SO₃M or —D; where-   T₁ and T₂ are C₁-C₅₀alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl,    ₇—C₁₈alkylaryl, C₆-C₁₈aryl, C₂-C₅₀alkenyl, C₅-C₁₂cycloalkenyl,    C₂-C₅₀alkynyl, C₅-C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl,    C₆-C₁₈bicycloalkenyl; or one of these radicals substituted by one or    more D and/or, if desired, interrupted by one or more units E;-   T₃ is C₁-C₅₀alkyl, C₂-C₅₀alkenyl, C₂-C₅₀alkynyl; or C₁-C₅₀alkyl,    C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl, C₇-C₁₈alkylaryl, C₆ —C₁₈aryl,    C₂-C₅₀alkenyl, C₅-C₁₂-cycloalkenyl, C₇-C₅₀alkynyl,    C₅-C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl, C₆-C₁₈bicycloalkenyl in each    case substituted by one or more —SOR, —SO₂R, —SO₂NRR′, —SO₃H, —SO₃M,    —COR, —COOR, —COOM, —CONRR′, —OCOR, —OCOOR, —OCONRR′, —NRCOR′    —NRCOOR′, —NRCONR′R″;-   T₄ is C₁-C₅₀alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl,    C₇-C₁₈alkylaryl, C₅-C₁₈aryl, C₂-C₆₀alkenyl, C₅-C₁₂-cycloalkenyl,    C₂-C₅₀alkynyl, C₅-C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl,    C₆-C₁₈bicycloalkenyl in each case substituted by one or more —COOM    and, if desired, interrupted by one or more units E and/or    substituted by D;-   D is selected from —R, —OH, —OR, —SR, —NRR′, —NRSO₂R′, —SOR, —SO₂R,    —SO₂NRR′, —SO₃H, —SO₃M, -Hal, —CN, —COR, —COOR, —COOM, —CONRR′,    4COR, —OCOOR, —OCONRR′, —NRCOR′, —NRCOOR′, —NRCONR′R″;-   E is selected from —O—, —S—, —NR—, —SO—, —SO₂, SO₂NR—, —CO—, —COO—,    —CONR—, —OCO—, —O—COO—, OCONR—, —NRCO—, —NR—COO— and —NRCONR′—;-   R, R′, R″ independently of one another are H, C₁-C₅₀alkyl,    C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl, C₇-C₁₈alkylaryl, C₆-C₁₈aryl,    C₂-C₅₀alkenyl, C₅-C₁₂cycloalkenyl, C₂-C₅₀alkynyl,    C₅-C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl, C₆-C₁₈bicycloalkenyl;-   Hal is —F, —Cl, —Br or —I;-   M is a monovalent metal cation, preferably an alkali metal cation,    or is N(RR′R″R*)⁺, especially ammonium, or is P(RR′R″ R*)⁺;    and in which, in the compound-   G₁, the radical R₁ is Q₁ and R₂, R₃, R₄, R₅ and R₈ are each    hydrogen;-   G₂, the radicals R₁ and R₂ independently of one another are each Q₂    and R₃, R₄, R₅ and R₅ are each hydrogen;-   G₃, the radicals R₁, R₂, and R₃ independently of one another are    each Q₃ and R₄, R₅ and R₅ are each hydrogen;-   G₄, the radicals R₁, R₂, R₃ and R₄ independently of one another are    each Q₃ and R₅ and R₆ are each hydrogen;-   G₅, the radicals R₁, R₂, R₃, R₄ and R₅ independently of one another    are each Q₃ and R₆ is hydrogen;-   G₆, the radicals R₁, R₂, R₃, R₄, R₅ and R₆ Independently of one    another are each Q₃; and-   Q₁ is —T₁, —COT₁, —COH, —COOT, or —CONT₁T₂; and-   Q₂ is —T₃, —COT₁, —COH, —COOT₁ or CONT₁T₂; and-   Q₃ is —T₄.

T₃ is preferably C₁-C₁₈alkyl, C₃-C₁₂alkenyl, C₃alkynyl; or C₁C₁₈alkyl,cyclohexyl, C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl in each casesubstituted by one or more —SO₃H, —SO₃M, —COOR, COOM, —CONRR′, OCOR,—OCONRR′, —NRCOR′, —NRCOOR, or —NRCONR′R″;

T₄ is preferably C₁-C₁₈alkyl, cyclohexyl, C₇-C₁₈phenylalkyl,C₇-C₁₈alkylphenyl, C₆-C₁₈phenyl in each case substituted by one or more—COOM.

Further preferred substituents of the novel compounds of the formula IIIare as indicated earlier on above for compounds G₁-G₆ of the formula I.

The invention further provides compositions comprising

-   A) an organic material sensitive to exposure to light, oxygen and/or    heat, and-   B) as stabilizer, a mixture of compounds of the formula I, and also    provides a method of stabilizing organic material with respect to    exposure to light, oxygen and/or heat, which comprises adding or    applying to said material the mixture of compounds of the invention,    and also provides for the use of a mixture of compounds of formula I    as stabilizers with respect to exposure to light, oxygen and/or    heat.

The mixture of the invention may be used to protect a diversity oforganic material sensitive to damage by light, heat, oxygen, etc.;examples include oils, fats, waxes, automobile finishes, woodcoatings,paints such as emulsion paints or paints for mineral constructionmaterials such as concrete or asphalt, for example, reprographicmaterial such as photographs, films, printing inks, and correspondingrecording materials, wood or material comprising wood, paper, leather,plastics and coatings thereon, textiles, cosmetics, sun protectioncompositions, greenhouse films, windows, window coatings or window films(solar films). Possibilities include both the protection of the materialitself, into which the stabilizer mixture of the invention isincorporated, and the protection of a material to which the stabilizermixture of the invention is applied either directly or in the form of aprotective layer. Examples of such protective layers include coatings,top layers of laminates, impregnated articles, and also covers, screensor packaging of all kinds. Possibilities thus also include, for example,the protection of seed, skin tissue, hair or hair colorations, or ofactive substances such as pesticides, herbicides or fungicides.

Of particular interest is the use in polymeric materials, as are presentin plastics, rubbers, paints, varnishes or adhesives. Where the materialto be stabilized comprises photographic material, its structure ispreferably as described in U.S. Pat. No. 5,538,840 from column 25 line60 to column 106 line 35, and the mixture of the invention of formula Iis employed in analogy to the employment of the compound of the formula(I) described in U.S. Pat. No. 5,538,840, and/or polymers prepared fromit; the sections of U.S. Pat. No. 5,538,840 referred to are consideredpart of the present description.

Stabilizers of the invention comprising compounds of the formula I ofthe carboxylate and/or sulfonate type are particularly suitable forstabilizing coating compositions or emulsion paints that are based onwater, and also inks for ink-jet printing.

Preferred materials which may be stabilized in accordance with theinvention are synthetic organic polymers, prepolymers and photographicmaterial. The term prepolymers is intended to denote those monomeric oroligomeric compounds which may be converted into the high molecular massform (polymer) under the influence of heat or radiation, for example UVradiation, electron beams or X-rays, and/or under the influence ofchemical components such as crosslinkers, couplers or catalysts.

The stabilizer of the invention is notable in particular for anoutstanding protective action and also a high level of compatibilitywith the organic material to be stabilized, and good processingproperties. Very particularly, it is suitable as a light stabilizer (UVabsorber).

Examples of polymers which may be stabilized in this way are thefollowing:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or α-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) Including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers. 8. Halogen-containingpolymers such as polychloroprene, chlorinated rubbers, chlorinated andbrominated copolymer of isobutylene-isoprene (halobutyl rubber),chlorinated or sulfo-chlorinated polyethylene, copolymers of ethyleneand chlorinated ethylene, epichlorohydrin homo- and copolymers,especially polymers of halogen-containing vinyl compounds, for examplepolyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,polyvinylidene fluoride, as well as copolymers thereof such as vinylchloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephithalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyimides, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins:

-   -   26. Crosslinked epoxy resins derived from aliphatic,        cycloaliphatic, heterocyclic or aromatic glycidyl compounds,        e.g. products of diglycidyl ethers of bisphenol A and bisphenol        F, which are crosslinked with customary hardeners such as        anhydrides or amines, with or without accelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

The amount of stabilizer to be used is guided by the organic material tobe stabilized and by the intended use of the stabilized material. Ingeneral, the composition of the invention contains from 0.01 to 15, inparticular from 0.05 to 10, and especially from 0.1 to 5 parts by weightof the stabilizer (component B) per 100 parts by weight of component A.

Besides the stabilizer of the formula I, the compositions of theinvention may comprise other stabilizers or other additions, such asantioxidants, further light stabilizers, metal deactivators, phosphitesor phosphonites, for example. Examples of these are the followingstabilizers:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethyl-phenol,2,6dioctadecyl-4-methylphenol, 2,4,6tricyclohexylphenol,2,6-di-tert-butyl-4-meth-oxy-methylphenol, nonylphenols which are linearor branched in the side chains, e.g. 2,6-di-nonyl-4-methylphenol,2,4dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyl-heptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1,5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6tert-butyl-2-methylphenol),4.4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2.2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5-methylbenzyl)-6-tert-butyl-1-4-methylphenyl]terophthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)₄-n-dodecylmercaptobutane,1,1,5,5-tetra(S-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O—, N—and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5di-tert-butylbenzylmercaptoacetate,tris(3,5di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-ter-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5tris(3,5di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso cyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of B-(3.5di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylol-propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or -poly-hydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3thiapentadecanol, trimethylhexanediol,trimethyl-olpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-[3-(3-tertbutyl-4-hydroxy-5methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

1.15. Esters of β-(3.5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9nonanediol, ethylene glycol,1,2propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, tri-ethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3.5di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard™XL-1, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxy-diphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoyl-aminophenol.4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5-(2-methoxy)carbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxy-phenyl)benzotriazole,2-(3-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂₂, whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′.(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4benzyloxy, 4,2′,4′-trihydroxy and2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano->methyl-β-methoxycinnamate, butylα-cyano-βmethyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-βcyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thiobis[4<1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5hydroxypyrazole, with or without additional ligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-di-chloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2.2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6 -dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6 trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [19226864-71]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro-[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly(methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2-dioctyloxy-5,5-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1.3.5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,214-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5triazine,2-[2-hydroxy-4-(2-hydroxy-3dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-4-butyl-4hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10tetra-tert-butyl-12-methyl-dibenz[d,g]-1, 3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2-dyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2-yl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy),tris(nonylphenyl) phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone,N-hexadecyl-alpha-heptadecylnitrone,N-ocatadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-hepta-decylnitrone,N-octadecyl-alpha-hexadecylnitrone, nitrone derived fromN,N-dialkylhydroxyl-amine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto benzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(βdodecylmercapto)propionate.

9. Polyamide stabilisers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene) sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A4316611;DE-A4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy) phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3(4-[2-hydroxyethoxy]-phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl-5,7-di-ten-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The nature and amount of the further stabilizers added is determined bythe nature of the substrate to be stabilized and by its intended use; inmany cases, from 0.1 to 5% by weight, based on the organic material tobe stabilized, is used.

With particular advantage, the stabilizer of the invention may be usedin compositions comprising as component A a synthetic organic polymer,especially a thermoplastic polymer, or a binder for coating materialssuch as paints, for example, or a reprographic material, especiallyphotographic material.

The reprographic material, especially colour photographic material, tobe stabilized with advantage in accordance with the present inventionis, for example, material as described in Research Disclosure 1990,31429 (pages 474-480), in USA-5538840 columns 26 to 106, inGB-A-2319523, or in DE-A-19750906, page 22, line 15, to page 105, line32. Preference is given to use in a layer comprising silver halide or inthe protective layer of a colour photographic material, especially of acolour film or of a colour photographic paper.

Suitable thermoplastic polymers include, for example, polyolefins (e.g.as per 1.-3. of the above list) and also polymers containing heteroatomsin the main chain, such as thermoplastic polymers containing nitrogen,oxygen and/or sulfur, especially nitrogen or oxygen, in the main chain;examples of such polymers are set out in the above list, inter alia,under 13.-20., with particular importance being possessed by polyamides,polyester and polycarbonate (17.-19.).

Incorporation into the synthetic organic polymers or prepolymers may beeffected by adding the stabilizer of the invention and any furtheradditives in accordance with the methods that are customary in the art.Incorporation may take place judiciously before or during shaping, forexample by mixing the pulverulent components or by adding the stabilizerto the melt or solution of the polymer, or by applying the dissolved ordispersed compounds to the polymer, with or without subsequentevaporation of the solvent. Elastomers may also be stabilized in theform of latices. A further possibility for incorporating the compoundsof the invention into polymers is to add them before or during thepolymerization of the corresponding monomers, and/or prior tocrosslinking.

The addition of the compounds or mixtures of the invention to theplastics to be stabilized may also take place in preformulated form, forexample in a form containing 2.5-98% by weight of the stabilizer of theinvention in addition to at least one other component, e.g. anemulsifier or dispersant, or in the form of a masterbatch containingthese compounds, for example, in a concentration of from 2.5 to 25% byweight.

The incorporation may judiciously be effected in accordance with thefollowing methods:

-   -   as an emulsion or dispersion (e.g. to latices or emulsion        polymers)    -   as a dry mixture during the mixing of additional components or        polymer mixtures    -   by direct addition to the processing apparatus (e.g. extruder,        internal mixer, etc.)    -   as a solution or melt.

The stabilized polymer compositions obtained in this way may beconverted by the customary methods, such as by hotpressing, spinning,extrusion or injection moulding, for example, into shaped articles, suchas fibres, films, strips, sheets, sandwich plates, vessels, pipes andother profiles, for example.

The invention therefore further provides the use of the polymercomposition of the invention for producing a shaped article.

Use in multilayer systems is also of interest. In this case, a polymercomposition of the invention comprising a relatively large amount ofstabilizer of formula I, for example 1-15% by weight, is applied in athin film (10-100 μm) to a shaped article made from a polymer containinglittle or no stabilizer of the invention. The application may besynchronous with the shaping of the base article, for example bycoextrusion. Alternatively, application may take place to the basearticle in its already shaped form, for example by lamination with afilm or by coating with a solution. The outer layer or outer layers ofthe finished article have the function of a UV filter which protects theinterior of the article against UV light. The outer layer preferablycontains 1-15% by weight, in particular 5-10% by weight, of at least onestabilizer of formula I.

The present invention therefore further provides for the use of thepolymer composition of the invention for producing multilayer systemswhere the outer layer(s) in a thickness of 10-100 μm comprises(comprise) a polymer composition of the invention while the inner layercontains little or no stabilizer of formula I.

The polymers thus stabilized are notable for high weathering stability,and in particular by high resistance to UV light. As a result, theyretain their mechanical properties and also their colour and their glossfor a long time, even when used outdoors.

Particular interest attaches to the use of the mixtures of the formula Iof the invention as stabilizers for coatings, for example for surfacecoatings. The invention therefore also provides those compositions whosecomponent A is a film forming binder.

The coating composition of the invention preferably contains 0.01-10parts by weight, in particular 0.05-10 parts by weight, especially 0.1-5parts by weight, of the stabilizer B of the invention per 100 parts byweight of solid binder A.

Here again, multilayer systems are possible, in which case theconcentration of component B in the top layer may be relatively high:for example, from 1 to 15 parts by weight, especially 310 parts byweight, of B per 100 parts by weight of solid binder A.

The use of the stabilizer of the invention in coatings provides theadditional advantage that delamination, i.e. the flaking of the coatingfrom the substrate, is prevented. This advantage is manifested inparticular in the case of metallic substrates, including multilayersystems on metallic substrates.

Suitable binders (component A) are in principle all of those common inthe art, examples being those as described in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th ed., Vol. A18, pp. 368-426, VCH, Weinheim1991. In general, the binder in question is a film-forming binder basedon a thermoplastic or thermosetting resin, predominantly on athermosetting resin. Examples of such are alkyd, acrylic, polyester,phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

Component A may be a cold curable or a heat curable binder, the additionof a curing catalyst may be advantageous. Suitable catalysts whichaccelerate the curing of the binder are described, for example, inUllmann's Encyclopedia of Industrial Chemistry, Vol. A18, p.469, VCHVerlagsgesellschaft, Weinheim 1991.

Preference is given to coating compositions wherein component A is abinder comprising a functional acrylic resin and a crosslinker.

Examples of coating compositions with specific binders are:

-   1. Coating materials based on cold or hot crosslinkable alkyd,    acrylic, polyester, epoxy or melamine resins or mixtures of such    resins, with or without the addition of a curing catalyst;-   2. Two component polyurethane coating materials based on    hydroxyl-containing acrylic, polyester or polyether resins and on    aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;-   3. One component polyurethane coating materials based on block    isocyanates, isocyanurates or polyisocyanates which are deblocked    during baking; if desired, the addition of melamine resins is also    possible;-   4. One component polyurethane coating materials based on aliphatic    or aromatic urethanes or polyurethanes and on hydroxyl-containing    acrylic, polyester or polyether resins;-   5. One component polyurethane coating materials based on aliphatic    or aromatic urethane acrylates or polyurethane acrylates having free    amine groups in the urethane structure and on melamine resins or    polyether resins, with or without addition of a curing catalyst;-   6. Two component coating materials based on (poly)ketimines and on    aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;-   7. Two component coating materials based on (poly)ketimines and on    an unsaturated acrylic resin or a polyacetoacetate resin or a    methacrylamidoglycolate methyl ester;-   8. Two component coating materials based on carboxyl- or    amino-containing polyacrylates and polyepoxides;-   9. Two component coating materials based on acrylic resins    containing anhydride groups and on a polyhydroxy or polyamino    component;-   10. Two component coating materials based on anhydrides containing    acrylate and on polyepoxides;-   11. Two component coating materials based on (poly)oxazolines and    acrylic resins containing anhydride groups, or unsaturated acrylic    resins, or aliphatic or aromatic isocyanates, isocyanurates or    polyisocyanates;-   12. Two component coating materials based on unsaturated    polyacrylates and polymalonates,-   13. Thermoplastic polyacrylate coating materials based on    thermoplastic acrylic resins or externally crosslinking acrylic    resins in combination with etherified melamine resins;-   14. Coating systems based on siloxane modified or fluorine modified    acrylic resins.

In addition to components A and B, the coating composition of theinvention preferably comprises as component C a light stabilizer of thesterically hindered amine, 2-(2-hydroxyphenyl)-1,3,5-triazine and/or2-hydroxyphenyl-2H benzotriazole type, as set out for example in theabove list under sections 2.1, 2.6 and 2.8. In this context, there isparticular technical interest in the addition of2-mono-resorcinyl-4,6-diaryl-1,3,5-triazines and/or 2-hydroxyphenyl-2H-benzotriazoles.

In order to achieve maximum light stability, there is particularinterest in the addition of sterically hindered amines, as set out inthe above list under 2.6. The invention therefore additionally providesa coating composition which besides components A and B comprises ascomponent C a light stabilizer of the sterically hindered amine type.

The stabilizer in question is preferably a 2,2,6,6-tetraalkylpiperidinederivative containing at least one group of the formula

in which R is hydrogen or methyl, especially hydrogen.

Component C is used preferably in an amount of 0.05-5 parts by weightper 100 parts by weight of the solid binder.

Examples of tetraalkylpiperidine derivatives which may be used ascomponent C may be taken from EP-A-356677, pages 3-17, sections a) tof). The stated sections of this EP-A are considered part of the presentdescription. It is particularly judicious to use the followingtetraalkylpiperidine derivatives:

-   Bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate,-   Bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,-   Bis(1,2,2,6-pentamethylpiperidin-4-yl) sebacate,-   Di(1,2,2,6,6pentamethylpiperidin-4-yl)    butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,-   Bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,-   Tetra(2,2,6,6-tetramethylpiperidin-4-yl)    butane-1,2,3,4-tetracarboxylate,-   Tetra(1,2,2,6,6-pentamethylpiperidin-4-yl)    butane-1,2,3,4-tetracarboxylate,-   2,2,4,4-Tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane,-   8-Acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4,5]    decane-2,4-dione,-   1,1-Bis(1,2,2,6,6-pentamethylpiperidin-4-yl-oxycarbonyl)-2-(4-methoxyphenyl)ethene,    or a compound of the formulae    where m is 550.

Besides the components A, B and, if present, C, the coating compositionmay comprise further components, examples being solvents, pigments,dyes, plasticizers, stabilizers, thixotropic agents, drying catalysts,and/or levelling assistants.

Examples of possible components are those described in Ullmann'sEncyclopedia of Industrial Chemistry, 5th Ed, Vol. A18, pp. 429471, VCH,Weinheim 1991.

Possible drying catalysts and curing catalysts are, for example,organometallic compounds, amines, amino-containing resins and/orphosphines. Examples of organometallic compounds are metal carboxylates,especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metalchelates, especially those of the metals Al, Ti or Zr, or organometalliccompounds such as organotin compounds, for example.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, theoctoates of Co, Zn or Cu, the naphthenates of Mn and Co, or thecorresponding linoleates, resinates or tallates.

Examples of metal chelates are the aluminium, titanium or zirconiumchelates of acetylacetone, ethyl acetylacetate, salicylaldehyde,salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate,and the alkoxides of these metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltindilaurate and dibutyltin dioctoate.

Examples of amines are especially tertiary amines, such astributylamine, triethanolamine, N-methyldiethanolamine,N-dimethylethanolamine, N-ethyl morpholine, N-methylmorpholine ordiazabicyclooctane (triethylenediamine), and their salts. Furtherexamples are quaternary ammonium salts, such as trimethylbenzylammoniumchloride, for example.

Resins containing amino groups are simultaneously binders and curingcatalysts. Examples thereof are amino-containing acrylate copolymers.

As curing catalysts it is also possible to use phosphines, such astriphenylphosphine.

The coating compositions of the invention may also comprise radiationcurable coating compositions. In this case, the binder essentiallycomprises monomeric or oligomeric compounds having ethylenicallyunsaturated bonds (prepolymers) which following application arecured—that is, converted into a crosslinked, high molecular mass form—bymeans of actinic radiation. Where the system in question is a UV curingsystem, it generally further comprises a photoinitiator.

Corresponding systems are described in the abovementioned publication,Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed, Vol. A18, pages451-453. In radiation curable coating compositions, the stabilizers ofthe invention may be used even without the addition of stericallyhindered amines.

The coating compositions of the invention may be applied to any desiredsubstrates, examples being metal, wood, plastic, or ceramic materials.In the case of automotive coating systems, they are preferably used asbasecoat material. Where the topcoat comprises two layers of which thebottom layer is pigmented and the top layer is not pigmented, thecoating composition of the invention may be used for the top or thebottom layer or for both layers, but preferably for the bottom(pigmented) layer.

Likewise preferred is the use of the compounds of the invention in woodpreservation, for example by incorporation of the stabilizer of theformula I into a varnish, stain or impregnant for wood. The presentinvention therefore further provides a method of stabilizing a woodsurface against damaging weathering effects, especially of light, oxygenand/or heat, which comprises treating the wood with a stabilizer of theformula I, in particular by applying a varnish, stain and/or impregnantcomprising a stabilizer of the formula I. With the aid of the method ofthe invention it is possible to achieve marked reductions in unwanteddiscolorations such as yellowing or bleaching of the wood. Mixtures ofcompounds of the formula I are preferably used as part of an impregnant,a stain, or a topcoat.

In the case of application to wood, it is also possible to use acompound of the formula I in which R₉ has one of the definitions givenfor R₁₁, an example being the compound 1 (2,4,6tris(2-hydroxy-4-[1-ethyloxycarbonyl-1-methylethoxy]phenyl)-1,3,5triazine).Preferred compounds in these compositions are as indicated earlier onabove.

Often, hindered amines are used at the same time, examples being thoseas described earlier on above, especially in amounts of 0.1-10%, e.g.0.2-5%, in particular 0.2-2% based on the overall weight of binder andsolvent. Particular preference for wood applications is given tohindered amines of the hydroxylamine type (as described in EP-A-309401,for example) or corresponding N-oxides, and also salts of thesecompounds.

Where application is made in the form of a stain or impregnant, it ispreferred to use the solvent selected, for example, from aliphatic,cycloaliphatic and/or aromatic hydrocarbons, alcohols, ethers, esters,ketones, glycols, glycol ethers, glycol esters, polyglycols or mixturesthereof. In this case the binder is preferably an alkyd resin, modifiedalkyd resin, self-crosslinking or non self-crosslinking acrylic resin, apolyester resin, an oxidatively drying oil, a phenolic resin,nitrocellulose, or a corresponding mixture.

Customary additives such as fungicides or insecticides are possible,e.g. tributylin oxide, phenylmercury salts, copper naphthenate,1-chloronaphthalene, pentachlorophenol, dieldrin, lindane, azaconazole,cypermethrin, benzalkonium hydrochloride, propiconazole or parathion.

Topcoats on wood normally comprise a binder, dissolved or dispersed inan organic solvent or water or mixture of an organic solvent and water.The binder is typically a resin which is airdrying or cures at roomtemperature (i.e. in the range approximately 10-30° C.). Examples ofsuch binders are nitrocellulose, polyvinyl acetate, polyvinyl chloride,unsaturated polyester resins, polyacrylates, polyurethanes, epoxyresins, phenolic resins, and especially alkyd resins. Also possible arecorresponding mixtures and also radiation-curable and/or solvent freesystems; illustrative examples are mixtures of acrylates ormethacrylates, unsaturated polyester/styrene mixtures, or mixtures ofother ethylenically unsaturated monomers or oligomers.

Examples of wood surfaces treated in accordance with the invention arethose of furniture, woodblock flooring, panels and wood veneers, alongwith exterior applications such as fences, constructional elements, woodfacings, window frames or door frames, etc.

The coating compositions of the invention may be applied to thesubstrates by the customary methods, for example by brushing, spraying,flowcoating, dipping or electrophoresis; see also Ullmann's Encyclopediaof Industrial Chemistry, 5th Ed., Vol. A118, pp. 491-500.

Depending on the binder system, the coatings may be cured at roomtemperature or by heating. Preferably, the coatings are cured at 50150°C., powder coatings or coil coatings also at higher temperatures.

The coatings obtained in accordance with the invention have anoutstanding resistance to harmful influences of light, oxygen and heat;reference should be made in particular to the good light stability andweathering stability of the coatings thus obtained, for example surfacecoatings.

The invention therefore also provides a coating, especially a surfacecoating, which is stabilized against harmful influences of light, oxygenand heat as a result of the addition of a compound of the formula I. Thesurface coating is preferably a basecoat for automobiles or a woodcoating. The invention further embraces a method of stabilizing acoating based on organic polymers against damage by light, oxygen and/orheat, which comprises admixing with the coating composition a compoundof the formula I, and also provides for the use of compounds of theformula I in coating compositions as stabilizers against damage bylight, oxygen and/or heat.

The coating compositions may comprise an organic solvent or solventmixture in which the binder is soluble. Alternatively, the coatingcomposition may be an aqueous solution or dispersion. The vehicle mayalso be a mixture of an organic solvent and water. The coatingcomposition may also be a high solids coating material or may besolvent-free (e.g. powder coating). Powder coatings are those, forexample, as described in Ullmann's Encyclopedia of Industrial Chemistry,5th Ed., A18, pages 438-444. The powder coating may also be present inthe form of a powder slurry, i.e. a dispersion of the powder, preferablyin water.

The pigments may be organic, inorganic or metallic pigments. Preferably,the coating compositions of the invention contain no pigments and areused as clearcoat.

Preference is likewise given to the use of the coating composition as abasecoat for applications in the automotive industry, especially as thepigmented topcoat of the coating. The use for coats lying above this,however, is also possible.

The following examples provide a further description of the inventionwithout representing any restriction. Parts and percentages therein areby weight; it an example mentions room temperature, it means atemperature in the range 20-25° C. In the case of solvent mixtures, suchas for chromatography, parts by volume are stated. These provisionsapply unless different details are given.

Abbreviations: THF tetrahydrofuran abs. anhydrous m.p. melting point ormelting range NMR nucleomagnetic resonance torr = mmHg (1 torrcorresponds to about 133 Pa) T_(g) glass transition temperature h hours

EXAMPLE 1 UV-Absorber Mixture Comprising2-(2,4dihydroxyphenyl)-4,6-bis(2-hydroxy-4(1-methoxycarbonylpentoxy)phenyl)-1,3,5-triazine,2,4,6-tris(2-hydroxy-4-(1-methoxycarbonyl-pentoxy)phenyl)-1,3,5triazineand 2-(2,4-di(methoxycarbonylpentoxy)phenyl)-4.6-bis(2-hydroxy4(1-methoxycarbonylpentoxy)phenyl)1,3,54triazine

12.15 g of tris(2.4-dihydroxyphenyl)-1,3,5-triazine, 10.5 g of sodiumcarbonate, 20 ml of dimethylformamide and 20.15 g (96.4 mmol) of methylbromocaproate are heated at 90° C. for 5 h with stirring. The reactionmixture is subsequently admixed with water and subjected to extractionwith heptane and the extracts are concentrated to give 23.78 g of abright orange coloured resin comprising the following components:

Similar results are obtained if extraction is carried out using, insteadof heptane, one of the solvents benzene, toluene, xylene, butyl acetate,ethyl acetate, ethyl methyl ketone, methyl isobutyl ketone or mixturesthereof or mixtures with heptane.

EXAMPLE 2

Working as in Example 1 but starting fromtris(2,4-dihydroxyphenyl)-1,3,5-triazine and ethyl bromoacetate gives amixture comprising:

EXAMPLE 3

Working as in Example 1 but starting fromtris(2,4-dihydroxyphenyl)-1,3,5triazine and ethyl 2-bromooctanoate givesa mixture comprising:

EXAMPLE 4

Working as in Example 1 but starting fromtris(2,4-dihydroxyphenyl)-1,3,5-triazine and methyl 2-bromopropionategives a mixture comprising:

EXAMPLE 4a

Working as in Example 1 but starting fromtris(2,4-dihydroxyphenyl-1,3,5-triazine and the equivalent amount of theester of an octanol isomer mixture of straight-chain and branched-chainC₇, C₈ and C₉ alcohols and bromopropionic acid gives the mixturecomprising the components of the following formulae:

iC₈H₁₇: C₇-C₉alkyl isomer mixture, Yield: 95%.

EXAMPLE 4b

10 g of tris(2,4-dihydroxyphenyl)-1,3,5-triazine, 8.89 g of Nacarbonate, 20 ml of dimethylformamide and 17.97 g of α-chloropropionicesters (isomer mixture of C₇-C₉alcohols in analogy to Example 4a) and 40ml of toluene are heated at 90° C. for 18 h with stirring. Aftercooling, water is added and the mixture is subjected to extraction withethyl acetate. The organic phase is washed a number of times with waterand dried. Removal of the solvent gives the product mixture in 77% yieldwith the principal components stated in Example 4a, containing 31% ofthe bisalkylated (A), 16% of the trisalkylated (B) and 2% of thetetraalkylated product (C) (HPLC, ¹H-NMR) as well as monoalkylatedproduct and starting material.

EXAMPLE 4c

10 g of tris(2,4-dihydroxyphenyl)-1,3,5triazine, 8.89 g of Na carbonate,20 ml of dimethylformamide and 17.97 g of α-chloropropionic esters as inExample 4b are heated at 100° C. for 20 h. After cooling, water is addedand the mixture is subjected to extraction with ethyl acetate. Theorganic phase is washed a number of times with water and dried. Removalof the solvent gives the product mixture as in Example 4a as anorange-coloured resin in 96% yield containing 10% (A), 36% (B) and 42%(C) (HPLC, ¹H-NMR) as well as monoalkylated products and startingmaterial.

EXAMPLE 4d

10 g of tris(2,4-dihydroxyphenyl)-1,3,5-triazine containing 3equivalents of dimethylacetamide, 5.40 g of Na carbonate, 13 ml ofdimethylformamide and 13.26 g of α-bromopropionic esters (isomer mixtureof C₇-C₉alcohols as in Example 4a) and 13 ml of heptane are heated at90° C. for 7 h with stirring. After cooling, water is added and themixture is subjected to extraction with heptane and ethyl acetate. Theorganic phase is washed a number of times with salt water and water andthen dried. Removal of the solvent gives the product mixture as inExample 4a, quantitatively, as an orange-coloured resin containing 30%(A), 41% (B) and 15% (C) (HPLC, ¹H-NMR) as well as monoalkylated productand starting material.

EXAMPLE 4e

10 g of tris(2,4-dihydroxyphenyl)-1,3,5-triazine containing 3equivalents of dimethylacetamide, 5.40 g of Na carbonate, 13 ml ofdimethylformamide and 13.26 g of α-bromopropionic esters (isomer mixtureof C₇-C₉alcohols as in Example 4a) and 13 ml of toluene are heated at90° C. for 7 h with stirring. After cooling, water is added and themixture is subjected to extraction with toluene. The organic phase iswashed a number of times with water and then dried. Removal of thesolvent gives the product mixture as in Example 4a as an orange-colouredresin containing 12% (A), 58% (B) and 28% (C) (HPLC, ¹H-NMR) as well asmonoalkylated product and starting material; yield 98%.

EXAMPLE 4f

300 g of tris-(2,4-dihydroxyphenyl)-1,3,5-triazine and 258.85 g sodiumcarbonate are mixed together with 776 ml dimethylformamide and thenstirred and heated for 2.5 hours to 130° C. Then the reaction mixture iscooled to 80° C. and a mixture of 539.1 g α-chloropropionic acidoctylester isomer mixture (prepared from 2-chloropropionicacid and amixture of branched and straight C₇, C₈ and C₉ alcohols) in 776 mlEthylmethylketone is added drop wise in 20 minutes.

The reaction mixture is stirred overnight at 80° C. Then it is cooled toroom temperature and filtered. To the filtrate are added 200 ml oftoluene and 2000 ml of water. The phases are separated and the organicphase is washed two times with 1000 ml of water. Then the organic phaseis dried over MgSO₄, filtered, and the solvents evaporated, giving anorange resin with 80% yield containing 22.1% bis-alkylated product A,34.1% tris-alkylated product B and 11.9% tetra-alkylated product Cdetermined by HPLC and ¹H-NMR besides mono-alkylated product andstarting material.

iC₆H₁₇: branched and straight heptyl, octyl and nonyl alkyl isomermixture

EXAMPLE 5 UV-Absorber Mixture Comprising2-(2,4-dihydroxyphenyl)-4,6-bis-(2-hydroxy-4-(1-hydroxycarbonylpentoxy)phenyl)-113,5-triazine,2,4,6-tris(2-hydroxy-4-(1-hydroxycarbonyl-pentoxy)phenyl)-1,3,5-triazineand2-(2,4-di(hydroxycarbonylpentoxy)phenyl)-4,6-bis(2-hydroxy-4-(1-hydroxycarbonylpentoxy)phenyl)-1,3,5-triazine

11.5 g of the mixture of compounds from Example 1 are dissolved in 10 mlof DMF at 100° C.

Then a solution of 4.08 g of NaOH in 30 ml of water is added and thereaction mixture is stirred overnight at 100° C. The reaction mixture isneutralized and filtered. The residue is washed with water and dried.This gives 12.32 g of a yellow powder mixture comprising the followingcomponents:

EXAMPLE 6

Working as in Example 5 but starting from the product from Example 2gives a mixture comprising:

EXAMPLE 7

Working as in Example 5 but starting from the product from Example 3gives a mixture comprising:

EXAMPLE 8

Working as in Example 5 but starting from the product from Example 4gives a mixture comprising:

EXAMPLE 9 UV-Absorber Mixture Comprising2-(2,4-dihydroxyphenyl)-4,6-bis(2-hydroxy-4-(1-potassium-oxycarbonylethoxy)phenyl)-1,3,5-triazine,2,4,6-tris(2-hydroxy-4-(1-potassium-oxycarbonylethoxy)phenyl)-1,3,5-triazineand2-(2,4-di(potassium-oxycarbonylethoxy)-phenyl)-4,6-bis(2-hydroxy-4-(1-potassium-oxycarbonylethoxy)phenyl)-1,3,5-triazine

5 g of the mixture of compounds from Example 8 are added to a solutionof 1.45 g of KOH in 30 ml of water and the mixture is stirred at roomtemperature for one hour. It is filtered to give a clear aqueousorange-coloured solution which comprises the following components:

EXAMPLE 10

Working as in Example 9 but starting from the product from Example 6 andwith NaOH as base gives a mixture comprising:

EXAMPLE 11 Surface Treatment of Wood

-   a) Impregnation: 0.5%, relative to the weight of the overall    formulation, of the stabilizer of example 4f is added to a    commercially available impregnant (Xylamon incolore™; manufacturer:    Sepam).

The impregnant is applied by brush to spruce boards (1 application) anddried at room temperature for 24 hours.

b) Topcoat: a topcoat is prepared from: 53.48 parts by weight of alkydresin (Jägalyd Antihydro ™, E. Jäger KG, 60% solution in white spirit);10.69 parts by weight of a thixotropic auxiliary (Jägalyd Antihydro-Thix ™, E. Jäger KG, 50% solution); 1.92 parts by weight of accelerator(Jäger Antihydro-Trockner ™); 33.44 parts by weight of solvent(Terlitol ™ 30); 0.32 part by weight of anti-skinning agent (Ascinin ™P, BAYER); 0.15 part by weight of anti-skinning agent (Luactin ™ M,BASF).

The topcoat is stabilized by addition of 1.0% of stabilizer of example4f and 1.0% of the compound in formula T1

(light stabilizer of the hindered amine type, Ciba Specialty Chemicals),amounts in each case based on the solids content of the binder. Acomparative sample is prepared without addition of the abovementionedstabilizers.

The topcoat is applied by brush (3 applications) to the impregnatedspruce boards with drying at room temperature for 24 hours after eachapplication.

Subsequently, the samples are subjected to accelerated weathering: UV-Alamps with maximum light intensity at 340 nm; weathering cycle: 5 hlight at 58° C., 1 h spraying at 22° C.

After the stated period of weathering, the colour change ΔE isdetermined in accordance with DIN 6174; the comparison used is anunweathered sample with unstabilized impregnant and unstabilizedtopcoat. The results show excellent stabilization of the samplesstabilized with the mixture of compounds according to Example 4f.

EXAMPLE 11a

A topcoat is prepared as described in Example 11 and applied topretreated spruce boards, either using no light stabilizer of thehindered amine type or using the compound of the formula Ti. Thecomparison used is an unstabilized topcoat. The tables below show theresults (AE in accordance with DIN 6174) after the stated period ofweathering. Stated amounts of stabilizer relate in each case to theweight of the solid coating.

Sample a: Accelerated weathering as in Example 11 but permanent lightexposure without spraying.

TABLE A Colour change ΔE after 1000 h exposure Additive ΔE none 29 2%comp. from Example 4f 11

Sample b: Accelerated weathering as in Example 11.

TABLE B Colour change ΔE after 1200 h accelerated weathering Additive ΔEnone 31 1% comp. from Example 4f + 1% T1 23

The results show excellent stabilization of the samples stabilized withthe mixture of the invention.

EXAMPLE 12 Stabilization of a 2-Coat Metallic Finish

The stabilizer of the invention to be tested is incorporated into 30 gof Solvesso® 100⁴⁾ and tested in a clearcoat of the followingcomposition (parts by weight):

Synthacryl ® SC 303¹⁾ 27.51 Synthacryl ® SC 370²⁾ 23.34 Maprenal ® 650³⁾27.29 Butyl acetate/butanol (37/8) 4.33 Isobutanol 4.87 Solvesso ® 150⁴⁾2.72 Kristallöl K-30⁵⁾ 8.74 Levelling assistant Baysilone ® MA⁶⁾ 1.2100.00 ¹⁾Acrylic resin, Hoechst AG; 65% solution in xylene/butanol(26/9)

-   1) Acrylic resin, Hoechst AG; 65% solution in xylene/butanol (26/9)-   2) Acrylic resin, Hoechst AG; 75% solution in Solvesso® 100⁴⁾-   3) Melamine resin, Hoechst AG; 55% solution in isobutanol-   4) Mixture of aromatic hydrocarbons (manufacturer: Esso); boiling    range 182-203° C. (Solvesso® 150) or 161-178° C. (Solvesso® 100)-   5) Mixture of aliphatic hydrocarbons (manufacturer Shell); boiling    range: 145-200° C.-   6) 1% in Solvesso® 150⁴⁾ (manufacturer: Bayer AG)

1.5% by weight of the mixture of compounds from Example 1 or Example 3or Example 4a in each case are added to the clearcoat; in some samples,an additional 0.7% of the compound

(compound A) is incorporated (amounts in each case based on the solidscontent of the coating). The comparison used is a clearcoat containingno light stabilizer.

The clearcoat is diluted with Solvesso® 100 to spray viscosity andsprayed onto a prepared aluminium panel (Uniprime® epoxy,silver-metallic basecoat) which is baked at 130° C. for 30 minutes. Theresult is a dry film thickness of 40-50 μm clearcoat.

The samples are then weathered in an UVCON® weathering apparatus fromAtlas Corp. (UVB-313 lamps) with a cycle of 4 h UV exposure at 70° C.and 4 h condensation at 50° C.

The samples are examined at regular intervals for gloss (20″ gloss inaccordance with DIN 67530) and freedom from cracks. The samplesstabilized in accordance with the invention exhibit a markedly betterweathering stability (gloss retention, crack resistance) than theunstabilized comparison sample.

EXAMPLE 13 Solubility in Adhesives

To measure the solubility, the compound under test is added to a typicaladhesive GELVA® 263 (Solutia; a 44.5% strength solution of apolyacrylate in a mixture of ethyl acetate and hexane, the polyacrylatebeing a copolymer of methyl methacrylate, 2-ethylhexyl methacrylate andglycidyl methacrylate).

The test compound is dissolved in 5 ml of ethyl acetate, toluene or amixture of ethyl acetate and toluene. 5 g of GELVA® 263 are admixed tothe solution, and 2-3 ml of the resulting solution are introduced intoindividual glass dishes. The solubility is subsequently determined fromthe observed crystallization following evaporation of the solvent withina period of a few hours to several weeks.

The solubility data reported in the table below are the observed maximumconcentrations at which there is still no sign of onset ofcrystallization, reported as the overall weight of the admixed triazinecompounds to GELVA® 263.

Compound Solubility (%) Example 4a 22.6 Comparison* 8.0 *The comparisonused was the single compound2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine(compound no. 4 from GB-A-2337049).

The data show a markedly better solubility in adhesives for the mixtureof compounds of the invention than for an Individual compound of similarstructure.

EXAMPLE 14 Solar Films

A polyurethane film is produced as follows: 26.2 g of butyl acetate, 5.8g of ethyl acetate and 0.4 g of 50% FC 430 are admixed to 595 g ofacrylic polyol RK 4037 at 75% solids content in methyl amyl ketone(DuPont; MW 7000-9000; OH number 145). 0.75 g of the compound Ti fromExample 11 (1% based on the solids content) is added. 0.9 g of Desmodur®N-3390 (aliphatic polyisocyanate, 90% solids content, Bayer) is added to2.43 g of this mixture. The UV absorber to be tested is incorporatedinto the acrylic polyol component. The formulation is applied byspincoating to a quartz disk (1000 rpm, 2 seconds). The coating (1.4mil) is cured at 260° F. for 30 minutes.

UV spectra are recorded using a λ-9 UV-spectrophotometer from PerkinElmer every 0.5 nm, at 120 mm/min with a gap width of 2 nm.

Loss of UV absorber by weathering is determined by measuring thelongwave absorption maximum every 200 h. Extinction at the longwaveabsorption maximum before the beginning of weathering is about 2.3.Weathering takes place in accordance with SAEJ 1960 (exterior automotiveweathering conditions): 0.55 W/m² at 340 nm using an inner and an outerborosilicate filter; 40 minutes of exposure dry, 20 minutes of exposurewet (front), then 60 minutes of exposure followed by 60 minutes withoutexposure, in each case with condensation (back); black panel temperature70° C.; relative atmospheric humidity 50-55% during exposure and 100%during darkness. The results are summarized in the table below; amountsare based on the weight of the overall formulation.

TABLE Extinction of the polyurethane film before and after 2012 hweathering Extinction UV Absorber Extinction before after weathering1.6% compound from Example 4a 2.33 1.83

The stabilizer of the invention exhibits good persistence in thepolyurethane film.

EXAMPLE 15 Application in Photographic Layers

Atop a polyester support, a gelatine layer of the following composition(per m²) is applied in the customary manner:

Component: Amount: Gelatine 1200 mg  Tricresyl phosphate 150 mg Curingagent  40 mg Wetting agent 100 mg Compound from Example 4a 300 mg

The curing agent used is the potassium salt of2-hydroxy-4,6-dichloro-1,3,5-triazine, the wetting agent sodium4,8-diisobutylnaphthalene-2-sulfonate.

The gelatine layer is dried at 20° C. for 7 days.

This gives a clear transparent layer having a maximum optical density of1.10 which is suitable for a photographic recording material, as a UVfilter layer, for example.

Clear layers may be obtained uniformly by halving the amount oftricresyl phosphate or by using dibutyl phthalate instead of tricresylphosphate.

EXAMPLE 16

The procedure described in Example- 15 is repeated but using a mixtureof 1 part by weight of the compound from Example 4a and 1 part by weightof the compound B.

Compound B corresponds to the formula

(compound no. 21 from GB-A-2319523).

Clear transparent layers are obtained which are suitable for aphotographic recording material, as a UV filter layer, for example.

EXAMPLE 17

Layers are prepared as described in Example 15. The samples are exposedin an Atlas exposure apparatus at 120 kJ/cm² and the decrease in densityat the longwave absorption maximum (λ_(max)) is determined. The resultsare summarized in the table below.

UVA of the Comparative Density Sample invention UVA Mass ratio λ_(max)decrease 3-1 — Comp. B — 346 nm 10% 3-2 Example 4a — — 354 nm 5% 3-3Example 4a Comp. B 10/90 346 nm 11% 3-4 Example 4a Comp. B 20/80 347 nm8% 3-5 Example 4a Comp. B 30/70 347 nm 7%

A UV filter layer comprising the compound of the invention exhibitsoutstanding light stability and is therefore suitable for the long-termlight protection of photographic layers.

EXAMPLE 18

A photographic material is produced with the following layerconstruction:

topmost layer red-sensitive layer second gelatine interlayergreen-sensitive layer first gelatine interlayer blue-sensitive layerpolyethylene base

The gelatine layers comprise the following components (per m² of basematerial),

Blue-Sensitive Layer

-   α-(Benzyl-4-ethoxyhydantoin-1-yl)-α-pivaloyl-2-chloro-5-[α-(2,4di-t-amylphenoxy)butanamido]acetanilide    (400 mg)-   α-(1-Butyl-phenylurazol-4-yl)-α-pivaloyl-5-(3-dodecanesulfonyl-2-methylpropanamido)-2-methoxyacetamide    (400 mg)-   Dibutyl phthalate (130 mg)-   Dinonyl phthalate (130 mg)-   Gelatine (1200 mg)-   1,5-Dioxa-3-ethyl-3-[β-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyloxymethyl]-8,10-diphenyl-9-thia-[5,5]spiroundecane(150    mg)-   Bis(1-acryloyl-2,2,6,6tetramethyl-4piperidyl)    2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate (150 mg)-   3,5-Di-t-butyl-4-hydroxy(2,4-di-t-amylphenyl)benzoate (150 mg)-   Poly(N-t-butylacrylamide) (50 mg)-   Blue-sensitive silver chlorobromide emulsion (240 mg)    First Gelatine Interlayer-   Gelatine (1000 mg)-   2-Di-t-octylhydroquinone (100 mg)-   Hexyl    5-[2,5-dihydroxy-4-(4-hexyloxycarbonyl-1,1-dimethylbutyl)phenyl]-5-methylhexanoate    (100 mg)-   Dibutyl phthalate (200 mg)-   Diisodecyl phthalate (200 mg)    Green-Sensitive Layer-   7-Chloro-2-{2-[2-(2,4-di-t-amylphenoxy)octanamido]-1-methylethyl}-6-methyl-1H-pyrazolo[1,5-b][1,2,4]triazole    (100 mg)-   6-t-Butyl-7chloro-3-(3-dodecanesulfonylpropyl)-1H-pyrazolo[5,1-o][1,2,4]triazole    (100 mg)-   Dibutyl phthalate (100 mg)-   Dicresyl phosphate (100 mg)-   Trioctyl phosphate (100 mg)-   Gelatine (1400 mg)-   3,3,3′,3′-Tetramethyl-5,5′,6,6′-tetrapropoxy-1,1′-spirobiindane (100    mg)-   4-(i-Tridecyloxyphenyl)thiomorpholine 1,1-dioxide (100 mg)-   4,4′-Butylidenebis(3-methyl-6t-butylphenol) (50 mg)-   2,2′-Isobutylidenebis(4,6-dimethylphenol) (10 mg)-   3,5-Dichloro-4-(hexadecyloxycarbonyloxy)ethylbenzoate (20 mg)-   3,5-Bis[3-(2,4-di-t-amylphenoxy)propylcarbamoyl]sodium    benzenesulfonate (20 mg)-   Green-sensitive silver chlorobromide emulsion (150 mg)    Second Gelatine Interlayer-   Gelatine (1000 mg)-   5-Chloro-2-(3,5-di-tbutyl-2-hydroxyphenyl)benzo-1,2,3-triazole (200    mg)-   2-(3-Dodecyl-2-hydroxy-5-methylphenyl)benzo-1,2,3-triazole (200 mg)-   Trinonyl phosphate (300 mg)-   2,5-Di-t-octylhydroquinone (50 mg)-   Hexyl    5-[2,5-dihydroxy-4-(4-hexyloxycarbonyl-1,1-dimethylbutyl)phenyl]-5-methylhexanoate    (50 mg)    Red-Sensitive Layer-   2-[a-(2,4-Di-t-amylphenoxy)butanamido]-4,6-di-chloro-5-ethylphenol    (150 mg)-   2,4-Dichloro-3-ethyl-6-hexadecanamidophenol (150 mg)-   4-Chloro-2-(1,2,3,4,5-pentafluorobenzamido)-5-[2-(2,4-di-t-amylphenoxy)-3    methylbutanamido]phenol (100 mg)-   Dioctyl phthalate (100 mg)-   Dicyclohexyl phthalate (100 mg)-   Gelatine (1200 mg)-   5-Chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)benzo-1,2,3-triazole (100    mg)-   2-(3-Dodecyl-2-hydroxy-5-methylphenyl)benzo-1,2,3-triazole (100 mg)-   3,5-Di-t-butyl-4-hydroxy(2,4-di-t-amylphenyl)benzoate (50 mg)-   Poly(N-t-butylacrylamide) (300 mg)-   N,N-Diethyl-2,4-di-t-amylphenoxyacetamide (100 mg)-   2,5-Di-t-octylhydroquinone (50 mg)-   Red-sensitive silver chlorobromide emulsion (200 mg)

The topmost layer is prepared with and without UV absorber;

With UV Absorber:

-   2,5-Di-t octylhydroquinone (20 mg)-   Hexyl    5-[2,5-dihydroxy-4-(4-hexyloxycarbonyl-1,1-dimethylbutyl)phenyl]-5-methylhexanoate    (20 mg)-   Gelatine (400 mg)-   Trinonyl phosphate (120 mg)-   UV absorber compound from Example 4a (200 mg)    Without UV Absorber:-   Gelatine (800 mg)

The curing agent used is 2,4-dichloro-6-hydroxytriazine K salt solution,the wetting agent the sodium salt of diisobutylnaphthalenesulfonic acid.

Exposed onto the samples (with blue, green or red light respectively)are in each case three step wedges with a density difference of 0.3 logE per stage. Subsequently, the samples are processed in accordance withprocess RA-4 (Kodak) for colour papers.

Following exposure and processing, the remission densities are measuredin the red for the cyan stage, in the green for the magenta stage and inthe blue for the yellow stage, at a density between 0.9 and 1.1 of thewedges. The wedges are then exposed with a total of 15 kJ/cm² in anAtlas exposure apparatus and the remission densities are measured again.

With the magenta wedge, additionally, the remission density is measuredin the blue before and after exposure, for the yellowing.

The presence of the compound of the invention in the topmost layerreduces the dye density loss of the cyan, magenta and yellow image dyeand also the yellowing of the magenta layer.

EXAMPLE 19 Light Stabilization of Printing Inks

An ink-jet printing ink is prepared by mixing together the followingcomponents:

-   -   2 g of Acid Red 52    -   20 g of diethylene glycol    -   78 g of water.

The ink is stirred until all of the components have dissolved and thesolution is then filtered through a Millipore filter with a pore size of0.45 mm.

One portion of the ink is inserted into an emptied and cleaned cartridgeof an HP DeskJet 510 printer. A printed sample is produced on paper fromthe company sihl+eika (ref. 193.178) (sample 1, comparison).

The compound of the invention (mixture) from Example 9 is tested bymixing 0.30 g of this compound with 2.70 g of the ink described aboveand using this mixture to produce a printed sample as described before(sample 2).

After drying, the colour density of the two sample prints are determinedwith a densitometer (Macbeth TR 924) using a status A filter.Subsequently, the sample prints are exposed in an Atlas Ci 35weathers-o-meter with an 81 klux xenon lamp through a 6 mm thick windowglass filter (dose: 3660 klux h). Following exposure, the colour densityis measured again in order to determine the percentage loss of colourdensity. The results are shown in the table below:

Colour density loss Sample Additive after 3660 klux h (%) 1 (Comparison)— 46 2 (Invention) Ex. 9 26

As the table shows the mixture of compounds of the inventionsignificantly improves the light stability of the dye.

1. A mixture of compounds comprising compounds G₂, G₃ and G₄ andoptionally, at least one further compound selected from the groupconsisting of G₀, G₁, G₃, G₄, G₅ and G₆, wherein G₂, G₃ and G₄ are eachpresent from 5-80 parts by weight, based on 100 parts by weight of thetotal of compounds G₀-G₆, and where the compounds G₀-G₆ each correspondto the formula I

in which X, Y and Z independently of one another are H, T₁, OT₁, NT₁T₂,ST₁, SOT₁, SO₂T₁, SO₂NT₁T₂, SO₃H, SO₃T₁, SO₃M or —D; where T₁ and T₂ areC₁-C₅₀alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl, C₇-C₁₈alkylaryl,C₆-C₁₈aryl, C₂-C₅₀alkenyl, C₅-C₁₂cycloalkenyl, C₂-C₅₀alkynyl,C₅C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl, C₆-C₁₈bicycloalkenyl; or one ofthese radicals substituted by one or more D and/or, if desired,interrupted by one or more units E; D is selected from the groupconsisting of —R, —OH, —OR, —SR, —NRR′, —NRSO₂R′, —SOR, —SO₂R, —SO₂NRR′,—SO₃H, —SO₃M, —SO₃R, oxiranyl, -Hal, —CN, —COR, —COOR, —COOM, —CONRR′,—OCOR, —OCOOR, —OCONRR′, —NRCOR′, —NRCOOR′, and —NRCONR′R″; E isselected from the group consisting of —O—, —S—, —NR—, —SO—, —SO₂—,—SO₂NR—, —CO—, —COO—, —CONR—, —OCO—, —O—CO—O—, OCONR—, —NRCO—, —NR—CO—O—and —NRCONR′—; R, R′, R″, R* independently of one another are H,C₁-C₅₀alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl, C₇-C₁₈alkylaryl,C₆-C₁₈aryl, C₂-C₅₀alkenyl, C₅-C₁₂cycloalkenyl, C₂-C₅₀alkynyl,C₅-C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl or C₆-C₁₈bicycloalkenyl; or areone of these aforementioned hydrocarbon radicals substituted by OHand/or interrupted by O; Hal is —F, —Cl, —Br or —I; M is a monovalentmetal cation or is N(RR′R″R*)⁺ or is P(RR′R″R*)⁺; and in which, in thecompound G₀, the radicals R₁, R₂, R₃, R₄, R₅and R₆ are each hydrogen;G₁, one radical from the group R₁, R₂, R₃, R₄, R₅and R₆is Q and theothers are each hydrogen; G₂, two radicals from the group R₁, R₂, R₃,R₄, R₅and R₆are each Q and the others are each hydrogen; G₃, threeradicals from the group R₁, R₂, R₃, R₄, R₅and R₆are each Q and theothers are each hydrogen; G₄, four radicals from the group R₁, R₂, R₃,R₄, R₅and R₆are each Q and the others are each hydrogen; G₅, fiveradicals from the group R₁, R₂, R₃, R₄, R₅and R₆are each Q and 1 radicalis hydrogen; G₆, the radicals R₁, R₂, R₃, R₄, R₅and R₆are each Q; and Qis —T₁, —COT₁, —COH, —COOT₁, —CONHT₁, —CONH₂ or —CONT₁T₂.
 2. A compoundmixture according to claim 1, comprising G₂and a further compound fromthe group G₀, G₁, G₃, G₄, G₅, G₆in each case in an amount of from 1 to99 parts by weight per 100 parts by weight of the total compoundsG₀-G₆present in the stabilizer mixture.
 3. A compound mixture accordingto claim 1, comprising G₂ and also G₃ and/or G₄ in each case in anamount of from 1 to 98 parts by weight per 100 parts by weight of thetotal compounds G₀-G₆ present in the mixture.
 4. A compound mixtureaccording to claim 1, in which, in the compounds G₁-G₆ of the formula I,X, Y and Z independently of one another are —H, —T₁, or D; T₁ and T₂independently of one another are C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl,C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl, naphthyl, biphenylyl,C₂-C₁₈alkenyl, C₅-C₁₂cycloalkenyl, C₂-C₁₂-alkynyl; or are C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, C-₇C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl,naphthyl, biphenylyl, C₂-C₁₈alkenyl, C₅-C₁₂cycloalkenyl, C₂-C₁₂alkynylin each case substituted by one or more D; or are C₂-C₅₀alkyl,C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, C₅-C₁₂-cycloalkyl,C₅-C₁₂cycloalkenyl or C₄-C₁₈alkenyl in each case interrupted by one ormore E; or are C₂-C₅₀alkyl, C₃-C₁₈alkenyl, C₇-C₁₋₈alkylphenyl,C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkenyl or C₇-C₁₈phenylalkyl which aresubstituted by D and interrupted by E; D is —R, —OH, —OR, —NRR′, -Hal,—CN, —COR, —COOR, —COOM, —CONRR′, —OCOR, —OCOOR, —OCONRR′, —NRCOR′,—NRCOOR′, —NRCONR′R″, oxiranyl, —SO₃H, —SO₃M; E is —O—, —NR—, —CO—,—COO—, —CONR—, —OCO—, —OCOO—, OCONR—, —NRCO—, —NRCOO—, —NRCONR′—; R, R′,R″, R* independently of one another are H, C₁-C₅₀alkyl,C₅-C₁₂cycloalkyl, C₇-C₁₈-phenylalkyl, C₇-C₁₈alkylphenyl, phenyl,naphthyl, biphenylyl, C₂-C₅₀alkenyl, C₅-C₁₂-cycloalkenyl, C₂-C₅₀alkynyl;Hal is —F or —Cl; and M is an alkali metal cation or N(RR′R″R*)⁺.
 5. Acompound mixture according to claim 1, in which, in the compounds G₁-G₆of the formula I, Q is —T₁, —COT₁ or —CONT₁T₂; X, Y and Z independentlyof one another are —H, —T₁, D; D is —R, —OH, —OR, -Hal, —COR, —COOR,—COOM, —CONRR′, —OCOR, —OCOOR, —OCONRR′, —SO₃H, —SO₃M; E is —O—, —CO—,—COO—, —CONR—, —OCO—, —OCOO—, OCONR—; R, R′, R″ independently of oneanother are H, C₁-C₁₈alkyl, cyclohexyl, cyclododecyl,C₇-C₁₈-phenylalkyl, C₇-C₁₈alkylphenyl, phenyl, C₂-C₁₂alkenyl; and Hal is—F or —Cl; and M is Li, Na or K.
 6. A compound mixture according toclaim 1, in which, in the compounds G₁-G₆ of the formula I, Q is —T₁,—COT₁, —CONT₁T₂; X, Y and Z independently of one another are —H, —T₁ or—D; T₁ and T₂ independently of one another are C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl,naphthyl, biphenylyl, C₂-C₁₈alkenyl; or are C₁-C₁₈alkyl, cyclohexyl,C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl, C₃-C₁₂alkenyl in each casesubstituted by D; or are C₃-C₅₀alkyl, C₇-C₁₈phenylalkyl,C₇-C₁₈alkylphenyl or C₄-C₁₈alkenyl interrupted by E; or are C₂-C₅₀alkylor C₄-C₁₈alkenyl or C₇-C₁₈phenylalkyl which are substituted by D andinterrupted by E; D is —R, —OH, —OR, -Hal, —COR″, —COOR, —COOM, —OCOR″,—SO₃H, —SO₃M; E is —O—, —CO—, —COO—, —OCO—; R is H, C₁-C₁₈alkyl,cyclohexyl, C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl, phenyl, C₃-C₁₂alkenyl;R″ is H, C₁-C₁₈alkyl, cyclohexyl, C₇-C₁₈phenylalkyl, C₇-C₁₈alkylphenyl,phenyl, C₃-C₁₂alkenyl; Hal is —F or —Cl; and M is Li, Na or K.
 7. Acomposition comprising A) an organic material sensitive to damage bylight, oxygen and/or heat, and B) as a stabilizer, a mixture ofcompounds according to claim
 1. 8. A composition according to claim 7,comprising from 0.01 to 15 parts by weight of component B per 100 partsby weight of component A.
 9. A composition according to claim 7, whereincomponent A is a thermoplastic polymer or a binder for coatings or areprographic material or wood or wood-containing material.
 10. Acomposition according to claim 7, further comprising an additiveselected from the group consisting of the antioxidants, UV absorbers andlight stabilizers, metal deactivators, phosphites and phosphonites,hydroxylamines, nitrones, thiosynergists, peroxide destroying compounds,polyamide stabilizers, basic costabilizers, nucleating agents, fillersand reinforcing agents, plasticizers, lubricants, emulsifiers,dispersants, pigments, rheological additives, catalysts, levellingassistants, optical brighteners, flame retardants, antistats, blowingagents, benzofuranones and indolinones.
 11. A composition according toclaim 7, further comprising one or more stabilizers selected from thegroup consisting of the sterically hindered amines,2-(2-hydroxyphenyl)-1,3,5-triazines, 2-hydroxyphenyl-2H-benzotriazoles,2-hydroxybenzophenones and oxalanilides.
 12. A method of stabilizingorganic material with respect to damaging exposure to light, oxygenand/or heat, which comprises admixing and/or applying to said materialas stabilizer a mixture of compounds according to claim
 1. 13. A methodof stabilizing organic material with respect to damaging exposure tolight, oxygen and/or heat, which comprises admixing and/or applying tosaid material as stabilizer a compound G₂, G₃, G₄, G₅ or G₆ of theformula III

in which X, Y and Z independently of one another are H, T₁, OT₁, NT₁T₂,ST₁, SOT₁, SO₂T₁, SO₂NT₁T₂, SO₃H SO₃T₁, SO₃M or —D; where T₁ and T₂ areC₁-C₅₀alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl, C₇-C₁₈alkylaryl,C₆-C₁₈aryl, C₂-C₅₀alkenyl, C₅-C₁₂cycloalkenyl, C₂-C₅₀alkynyl,C₅-C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl, C₆-C₁₈bicycloalkenyl; or one ofthese radicals substituted by one or more D and/or, if desired,interupted by one or more units E; T₃ is C₁-C₅₀alkyl, C₂-C₅₀alkenyl,C₂C₅₀alkynyl; or C₁-C₅₀alkyl C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl,C₇-C₁₈alkylaryl, C₆-C₁₈aryl, C₂-C₅₀alkenyl, C₅-C₁₂-cycloalkenyl,C₂-C₅₀alkynyl, C₅-C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl,C₆-C₁₈bicycloalkenyl in each case substituted by one or more —SOR,—SO₂R, —SO₂NRR′,—SO₃H,—SO₃M, —COR, —COOR, —COOM, —CONRR′, —OCOR, —OCOOR,—OCONRR′, —NRCOR′, —NRCOOR′, —NRCONR′R″; T₄ is C₁-C₅₀alkyl,C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl, C₇-C₁₈alkylaryl, C₆-C₁₈aryl,C₂-C₅₀alkenyl, C₅-C₁₂-cycloalkenyl, C₂-C₅₀alkynyl, C₅-C₁₂cycloalkynyl,C₅-C₁₈bicycloalkyl, C₆-C₁₈bicycloalkenyl in each case substituted by oneor more —COOM and, if desired, interrupted by one or more units E; D isselected from the group consisting of —R, —OH, —OR —SR, —NRR′, —NRSO₂R′,—SOR, —SO₂R, —SO₂NRR′, —SO₃H, —SO₃M, -Hal, —CN, —COR, —COOR, —COOM,—CONRR′, —OCOR, —OCOOR, —OCONRR′, —NRCOR′, —NRCOOR′ and —NRCONR′R″; E isselected from the group consisting of —O—, —S—, —NR—, —SO—, —SO₂—,—SO₂NR—, —CO—, —COO—, —CONR—, —OCO—, —O—COO—, OCONR—, —NRCO—, —NR—CO—O—and —NRCONR′—; R, R′, R″ independently of one another are H,C₁-C₅₀alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₈arylalkyl, C₇-C₁₈alkylaryl,C₆-C₁₈aryl, C₁-C₅₀alkenyl, C₅-C₁₂cycloalkenyl, C₂-C₅₀alkynyl,C₅-C₁₂cycloalkynyl, C₅-C₁₈bicycloalkyl or C₆-C₁₈bicycloalkenyl: Hal is—F, —Cl, —Br or —l; M is a monovalent metal cation or N(R)₄ ^(±) orP(R)₄ ⁺; and in which, in the compound G₁, the radical R₁ is Q₁ and R₂,R₃, R₄, R₅ and R₆ are each hydrogen: G₂, the radicals R₁ and R₂independently of one another are each Q₂ and R₃, R₄, R₅ and R₆ are eachhydrogen: G₃, the radicals R₁, R₂, and R₃ independently of one anotherare each Q₃ and R₄, R₅ and R₆ are each hydrogen; G₄, the radicals R₁,R₂, R₃ and R₄ independently of one another are each Q₃ and R₅ and R₆ areeach hydrogen; G₅, the radicals R₁ R₂, R₃, R₄ and R₅ independently ofone another are each Q₃ and R₆ is hydrogen; G₆, the radicals R₁, R₂, R₃R₄, R₅ and R₆ independently of one another are each Q₃; and Q₁ is —T₁,—COT₁, —COH, —COOT₁, or —CONT₁T₂; and Q₂, is —T₃, —COT₁, —COH, —COOT₁ or—CONT₁T₂; and Q₃ is —T₄.